Pesticidal 1-polyarylpyrazoles

ABSTRACT

A compound of formula (I):compositions containing them and methods of use to control pests.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No. 09/216,878, filed Dec. 21, 1998, now U.S. Pat. No. 6,107,322, which is a divisional of U.S. patent application Ser. No. 08/963,631, filed Nov. 4, 1997, now U.S. Pat. No. 5,922,884, which claims the priority of U.S. Provisional Patent Application No. 60/030,128, filed Nov. 4, 1996. All three prior applications are incorporated by reference herein in their entireties and relied upon.

The invention relates to new 1-arylpyrazoles and derivatives thereof which have some valuable properties either as pesticides or as intermediates to make other pesticides. The invention further pertains to compositions of said compounds and methods, using said compounds either as intermediates to make other pesticides, or for the control of pests particularly insects, in particular to the application of said compounds or compositions in agricultural methods of use or for animal protection, particularly as pesticides, for controlling arthropods.

International Patent Publication No. WO 87/03781 and European Patent Publication No. 295117, 154115, 201852 describe insecticidal 1-(substituted phenyl) pyrazoles. Other prior art is also found in the text of these patent applications or the patents issued therefrom.

International Patent Publications No. WO 93/06089 and WO 94/21606 also describe insecticidal 1-(4-SF₅ substituted phenyl) heterocycles which may be pyrroles as well as imidazoles or pyrazoles. The teaching of these patents is not substantially different from International Patent Publication No. WO 87/03781 or from European Patent Publication No. 0295117 as far as pyrazoles are concerned.

It is an object of the present invention to provide new pesticidal compounds of the 1-arylpyrazole family together with processes for their preparation.

Another object of the present invention is to provide pesticidal compositions and pesticidal methods of use of the pesticidal pyrazole compounds against arthropods, especially insects, particularly in agricultural or horticultural crops, forestry, veterinary medicine or livestock husbandry, or in public health.

A third object of the present invention is to provide very active compounds with broad spectrum pesticidal activity, as well as compounds with selective special activity, e.g., aphicidal, miticidal, foliar insecticidal, soil insecticidal, systemic, antifeeding or pesticidal activity via seed treatment.

A fourth object of the present invention is to provide compounds with substantially enhanced and more rapid activity, especially against insects and more particularly insects in their larval stages.

A fifth objective of the present invention is to provide compounds with greatly improved (faster and greater) penetration into pest species when topically applied and to thus provide enhanced movement of the compounds to the pesticidal site(s) of action within the pest.

These and other objectives of the invention are met in whole or part and shall become readily apparent from the description of the present invention which follows.

The invention thus relates to compounds having the general formula (I):

wherein:

X is N or C—R₂;

Y is N or C—R₃;

W is N or C—R₄;

R₂ and R₃ are independently selected from H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO₂, —S(O)_(n)R₈, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, aminosulfonyl, alkylarninosulfonyl, and dialkylaminosulfonyl;

R₄ is H, halogen, alkyl, alkoxy, CN, NO₂, haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, —CH═N—OH, —CH═N—O-alkyl, —S(NH₂)(═NH), —S(O)_(n)R₈, mercapto, haloalkylcarbonyl, or a —S— radical so that two molecules are bound together to form a disufide compound;

R₅ is hydrogen, halogen, —NR₉R₁₀, —N═CR₁₁R₁₉, —S(O)_(n)R₈, formyl, alkylcarbonyl, haloalkylcarbonyl, cyano,alkyl, haloalkyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl;

R₈ is alkyl or haloalkyl, alkenyl or alkynyl, or a cycloalkyl ring containing 3 to 5 carbon atoms;

R₁₁ is H, or alkyl;

R₁₉ may also be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino, or RIg is phenyl, thienyl, pyridyl or furyl, each of which is unsubstituted or substituted with alkyl, haloalkyl, halogen, NO₂, CN, alkoxy, haloalkoxy, OH, alkylcarbonyl, alkylcarbonyloxy;

R₉ and R₁₀ independent of one another are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈S(O)_(n), formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl; or are joined so as together form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably to form a morpholine, pyrrolidine, piperidine or piperazine ring; the alkyl portion of R₉ and R₁₀ may be substituted by R₇;

R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈S(O)_(n), —C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylarninocarbonyl, —CO₂H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl;

Z is N or C—R₁₆;

n is zero, one or two;

R₁₂, R₁₃, R₁₅, R₁₆, are independendy selected from hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfmyl, alkylsulf6nyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, foxmyl, alkylcarbonyl, alkoxycarbonyl;

R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, and alkoxycarbonyl, SF₅, R₈S(O)_(n); preferably R₂₄ is halogen, haloalkyl or haloalkoxy; or R₂₂ and R₂₃ or R₂₃ and R₂₄ or R₂₅ and R₂₆ may also be together a divinylidene group (—CH═CH—CH═CH—) or a methylene diether (—O—CH₂—O—) or halomethylene diether (—O—CF₂—O—) so as to form a cyclic ring vicinal to the phenyl ring; or pesticidally acceptable salts thereof.

By the term “pesticidally acceptable salts” is meant salts the anions and cations of which are known and accepted in the art for the formation of pesticidally acceptable salts. Preferably such salts are water soluble. Suitable acid addition salts formed from compounds of formula (I) containing an amine group, include salts with inorganic acids for example hydrochlorides, phosphates, sulfates and nitrates, and salts with organic acids for example acetates. Suitable salts with bases formed from compounds of formula (I) containing a suitably acidic group include alkali metal (for example sodium or potassium) salts, ammonium salts and organic amine (for example diethanolainine or morpholine) salts.

In the present invention, some words are used in a specific sense:

The term “lower alkyl —S(O)_(n)” means a radical of the formula —S(O)_(n)— lower alkyl. The term “R₁₀S(O)_(n)” means a radical of the formula —S(O)_(n)R₁₀. The term “aminocarbonyl” means a carbamoyl radical, that is, a radical of the formula —C(O)NH₂. Similarly, the term “alkylaminocarbonyl” means an alkylcarbamoyl radical, that is, a radical of the formula —C(O)—NH-alkyl; and the term “dialkylaminocarbonyl” means a dialkylcarbamoyl radical, that is, a radical of the formula —C(O)—N(alkyl)₂ in which the alkyl moieties can be the same or different. The term “aminosulfonyl” means a sulfamoyl radical, that is, —SO₂NH₂. Similarly, the term “alkylaminosulfonyl” means an alkylsulfamoyl radical, that is, a radical of the formula —SO₂NH-alkyl; while the term “dialkylaminosulfonyl” means a dialkylsulfamoyl radical, which has the formula —SO₂N(alkyl)₂ wherein the alkyl moieties can be the same or different.

The term “halo” before the name of a radical means that this radical is partially or completely halogenated, that is to say, substituted by F, Cl, Br, or I, in any combination, preferably by F or Cl. The term “halogen” means F, Cl, Br or I. The term “lower” before the name of a radical having a carbon skeleton means that this carbon skeleton has less than 6 carbon atoms. When the name of any substituent is repeated, it keeps the same meaning unless otherwise specified. The term “aryl” designates a carbon and/or heteroatom-containing aromatic radical which is preferably phenyl optionally substituted with one or more substituents selected from halogen, methyl and methoxy, especially phenyl, halophenyl, tolyl or xylyl. The term “aroyl” designates a carbonyl aromatic radical, that is, aryl-C(O)—, which is preferably a benzoyl, methylbenzoyl, halobenzoyl or xylylcarbonyl radical. The term “acyl” designates an alkylcarbonyl radical. The various individual radicals (such as alkyl, alkenyl, alkynyl, alkoxy and alkylene or the like) generally contain up to six carbon atoms.

A preferred class of compounds of formula (I) is that wherein

X is N;

Y is C—R₃;

W is C—R₄;

R₃ is H, halogen, hydroxy, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy, CN, NO₂, —S(O)_(n)R₈, alkylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, hydroxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl;

R₄ is H, halogen, alkyl, alkoxy, CN, NO₂, haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, —CH═N—OH, —CH═N—O-alkyl, —S(NH₂)(═NH), S(O)_(n)R₈, mercapto, haloalkylcarbonyl, or a —S— radical so that two molecules are bound together to form a disufide compound;

R₅ is hydrogen, halogen, —NR₉R₁₀, —N═CR₁₁R₁₉, —S(O)_(n)R₈, formyl, alkylcarbonyl, haloalkylcarbonyl, cyano, lower alkyl, hydrazino, alkoxycarbonyl, alkylthiocarbonyl, 1H-pyrrol-1-yl or 1H-pyrazol-1-yl, preferably, amino —NR₉R₁₀;

R₈ is alkyl or haloalkyl, alkenyl or alkynyl; or a cycloalkyl ring containing 3 to 5 carbon atoms; preferably R₈ is lower alkyl;

R₁₁ is H or alyl;

R₁₉ may also be hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino;

or R₁₉ is phenyl, thienyl, pyridyl or furyl, all of them being optionally substituted with alkyl, haloalkyl, halogen, NO₂, CN, alkoxy, haloalkoxy, OH, alkylcarbonyl, alkylcarbonyloxy;

R₉ and R₁₀ are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈—S(O)_(n), formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, aroyl; or are joined so as together form a divalent radical having 4 to 6 atoms in the chain, this divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, preferably to form a morpholine, pyrrolidine, piperidine or piperazine ring; the alkyl portion of R₉ and R₁₀ may be substituted by R₇;

R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈S(O)_(n), —C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylarninocarbonyl, dialkylaminocarbonyl, —CO₂H, halogen, hydroxy, arninosulfonyl, alkylaminosulfonyl or dialkylarninosulfonyl;

Z is N or C—R₁₆;

n is zero, one or two;

R₁₂, R₁₃, R₁₅, R₁₆, are separately hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl, alkoxycarbonyl;

R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, and alkoxycarbonyl, SF₅, R₈S(O)_(n), preferably, R₂₄ is halogen, haloalkyl or haloalkoxy; or R₂₂ and R₂₃ or R₂₃ and R₂₄ or R₂₅ and R₂₆ may also be together a divmylidene group (—CH═CH—CH═CH—) or a melhylenie diether (—O—CH₂—O—) or halomethylene diether (—O—CF₂—O—) so as to form a cyclic ring vicinal to the phenyl ring; or a pesticidally acceptable salt thereof.

Another preferred class of the compounds of formula (I) are those with one or more of the following features wherein:

X is N or C—R₂;

Y is N or C—R₃;

W is N or C—R₄;

R₃ is CN or halogen;

R₄ is H, halogen, formyl, or —S(O)_(n)R₈;

R₅ is hydrogen, halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl, or —NR₉R₁₀;

R₈ is methyl, ethyl, —CF₃, —CFCl₂, —CF₂Cl;

R₁₂ and R₁₆ are independently selected from F, Cl, Br and H;

R₁₃ and R₁₅ are H;

R₂₄ is —CF₃, —OCF₃, —CHF₂, —S(O)_(n)CF₃, —CFCl₂, —CF₂Cl, —OCF₂Cl, —OCFCl₂, Cl, Br or F; or

Z is CCl, CF, CBr or N.

A further especially preferred class of compounds are those wherein:

X is N;

Y is C—R₃;

W is C—R₄;

R₁₂ and R₁₆ are Cl or Br;

R₁₃ and R₁₅ are H;

R₂₄ is —CF₃, —OCF₃ or Br;

R₅ is amino;

R₉ and R₁₀ are H, alkyl or alkylcarbonyl;

R₈ is methyl or ethyl or CF₃, CCl₂F, CClF₂; and

R₃ is CN or halogen.

For the above preferred compounds, there are optimum combinations of substituent groups.

Further, preferred S(O)_(n)—R₈ substituents in formula (I) are: methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl, isopropylthio, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichloromethylsulfinyl, dichloromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.

Some compounds are useful as intermediates to make other pesticides, others are useful directly as pesticides. Compounds wherein R₂₃ or R₂₄ or R₂₅ is formyl are preferred as intermediates as well as compounds wherein R₅ is H or compounds wherein simultaneously R₄ is not halogenated and R₂₂ and R₂₃ and R₂₄ and R₂₅ and R₂₆are H.

The compounds of general formula (I) can be prepared by the application or adaptation of known methods (ie., methods heretofore used or described in the chemical literature including the Chemical Abstracts) employing as starting material the compounds of formula (II)

wherein the various substituents have the same meaning as in formula (I) and halo is a halogen atom, preferably bromine or iodine.

The compounds of formula (II) can be prepared by methods or processes similar to those described in International patent applications WO 87/03781, 93/06089, 94/21606, in European patent applications 295117, 403300, 385809, 0500209, 679650, 285,893, and 780,381, U.S. Pat. Nos. 5,232,940, 5,236,938, 5,187,185, 5,223,525 and German Patent application 19511269 or by other methods known to the skilled addressee. The skilled addressee understands and is generally knowledgeable of Chemical Abstracts. According to a first method of preparation of compounds of formula (I) from compounds of formula (II), a compound of formula (II) is caused to react with a boric acid or ester, preferably in presence of a coupling catalyst, so as to form a compound of formula (III)

wherein the substituents have the same meaning as previously indicated, and B(OR₃₀)₂ represents a boric acid or ester group (R₃₀ is preferably hydrogen, alkyl, or a divalent lower alkylene radical such that two R₃₀O radicals may form a cyclic borate ester),

said compound (III) being, in a second step, caused to react with a compound of formula (VI)

 wherein R₂₀ is bromine or iodine or O—SO₂CF₃.

The first step of this first process is generally and preferably conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether, the temperature is generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(0) or Pd₂ (dibenzylidene acetone)₃, generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine. The boron derivative used as a reactant with the compound of formula (II) is preferably a cyclic diboron ester or acid of formula (R₃₀O)₂B—B(OR₃₀)₂.

The second step of this first process is advantageously conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(0) or Pd₂ (dibenzylidene acetone)₃, generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine.

According to another method of preparation of compound of formula (I), a compound of formula (II) is caused to react with a compound of formula (IV):

wherein the substituents have the same meaning as previously indicated.

The process is generally and preferably conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(0) or Pd₂ (dibenzylidene acetone)₃, generally in the presence of a base such as an alkaline hydroxide or carbonate acetate ion or an amine.

According to still another method of preparation of compound of formula (I), a compound of formula (II) is caused to react in the presence of a catalyst as described above, with a hexaalkylstannane [(alkyl or cycloalkyl)₃Sn]₂ so as to form a compound of formula (V):

which in a second step is caused to react with a compound of formula (IV) in the presence of a coupling catalyst.

The first step of the process is generally conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; at a temperature generally between 50° C. and 150° C.; utilizing as catalysts organic derivatives of palladium including palladium acetate, tetrakis(triphenylphosphine)palladium(0) or Pd₂ (dibenzylidene acetone)₃.

The second step of this second process is generally conducted in an organic solvent, for example an hydrocarbon such as toluene or xylene; an amide such as dimethylformamide or N-methylpyrrolidone; an ether such as tetrahydrofuran, dimethoxyethane or 2-methoxyethylether; the temperature is generally between 50° C. and 150° C.; as catalysts, organic derivatives of palladium such as Pd (P-phenyl₃)₄, Pd₂ (dibenzylidene acetone)₃, Pd (O—CO—CH₃)₂ may be cited.

According to still another method of preparation of compound of formula (I), a compound of formula (II) is caused to react with a compound of formula (VII)

preferably in the presence of a coupling catalyst as described above, and preferably in a solvent as described above, and preferably at a temperature from 50° C. to 150° C.

According to another method of preparation of a compound of formula (I), a compound of formula (VIII):

is reacted in a step to form a pyrrole, inmidazole, triazole, or pyrazole of formula (I). Such reactions are known and can be found in Katritzky, Rees, and Scriven, Comprehensive Heterocyclic Chemistry II, volumes 2,3,4 1996, Pergamon Press, London.

The invention is illustrated by the following examples, which are not considered as limiting the invention but are given to better enable use of it.

EXAMPLE 1

Preparation of 1-[2,6-dichloro4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole.

A mixture of 6 g of 5-amiino-3-cyano-1-(2,6-dichloro-4-bromophenyl)-4-trifluoromethylthiopyrazole (prepared according to procedures reported in U.S. Pat. No. 5,232,940), 4-trifluoromethylphenylboronic acid (5.3 g), K₂CO₃ (5.8 g), tris-(dibenzylidene acetone) dipalladium (0.6 g) and diglyme was heated at 130° C. for 25 hours. After cooling to 20° C., the mixture was poured into water and extracted with diethyl ether. The ether solutions were combined, dried, filtered and the filtrate concentrated and purified by chromatography. The desired product as a solid (3.9 g, mp 181-184° C.) was obtained.

EXAMPLE 2

Preparation of 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-trifluoromethylsulfonyl-5-aminopyrazole.

A solution of 1-[2,6-dichloro-4(4-trifluoromethylphenyl)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole (0.5 g), m-chloroperbenzoic acid (2.2 g) and 1,2-dichloro-ethane was heated at reflux for 40 hours. After cooling to 20° C., the mixture was dissolved in diethyl ether and washed with sat. aqueous NaHCO₃ solution twice, then saturated aqueous NaHSO₃ solution twice, dried, filtered, and the filtrate concentrated and purified by chromatography. The desired product as a solid (0.13 g, mp 197-202° C.) was obtained.

EXAMPLE 3

Preparation of 1-[2,6-dichloro-4-(tributyltin)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole.

A mixture of 1-(2,6-dichloro-4bromophenyl)-3-cyano-4-trifluoromethylthio-5-aminopyrazole (5 g), bis-(tributyltin) (6.7 g), tetrakis(tri-phenylphosphine)palladium (0)(1.3 g) and 1-methyl-2-pyrrolidinone was heated to reflux for 75 minutes, cooled to 20° C., poured to water and extracted with methyl t-butyl ether. After concentrattion to dryness, methylene chloride was added and stirred with saturated aqueous KF solution for 16 hours. More water was added and extracted with methylene chloride. The methylene chloride solutions were combined, dried, filtered and the filtrate concentrated and purified via chromatography. The desired product as a solid (1.9 g, mp 116-117° C.) was obtained.

EXAMPLE 4

Preparation of 1-[2,6-dichloro-4-(2,3,5,6-tetrafluoropyrid-4-yl)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole.

A mixture of 1-[2,6-dichloro-4-(tributyltin)phenyl]-3-cyano-4-trifluoromethylthio-5-aminopyrazole (0.5 g), 4-bromo-2,3,5,6-tetrafluoropyridine (0.1 mL), tetrakis(tri-phenylphosphine) palladium (0)(0.1 g) and THF was refluxed for 26 hours. After cooling to 20° C., methylene chloride was added and stirred with saturated aqueous KF solution for 16 hours. The mixture was filtered with diethyl ether and dried, filtered again and the filtrate concentrated and purified via chromatography. The desired product as a solid (87 mg, mp 100-104° C.) was obtained.

EXAMPLE 5

Preparation of 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-5-aminopyrazole.

A mixture of 1-(2,6-dichloro-4-bromophenyl)-3-cyano-5-aminopyrazole (45 g, prepared according to procedures reported in U.S. Pat. No. 5,232,940), 4-trifluoromethylphenylboronic acid (45 g), 2 M of Na₂CO₃ (75 mL), tris-(dibenzylideneacetone) dipalladium (6.4 g), toluene and ethanol was heated at 130° C. for 25 hours. After cooling to 20° C., the mixture was poured into water and extracted with diethyl ether. The ether solutions were combined, dried, filtered and the filtrate concentrated and purified via chromatography. The desired product as a solid (30.6 g, mp 195-199° C.) was obtained.

EXAMPLE 6

Preparation of 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-bromo-5-aminopyrazole.

A mixture of 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-5-aminopyrazole (1 g), N-bromosuccinimide (0.5 g) and acetonitrile was stirred at 20° C. for 90 minutes, then concentrated and the residue was mixed with diethyl ether, washed with saturated aqueous NaHCO₃ solution, dried, filtered and the filtrate concentrated and purified via chromatography. The desired product as a solid (1.04 g, mp 178-180° C.) was obtained.

EXAMPLE 7

Preparation of 4-dichlorofluoromethylsulfenyl-1-[2-fluoro-4-(4-trifluoromethylphenyl)phenyl]imidazole.

Step A

A solution of 4-bromo-2-fluoroaniline (3.8 g) in 20 ml of triethyl orthoformate was stirred at room temperature. After stirring for 1 h, tetrahydrofuran (40 ml), aminoacetonitrile hydrochloride (2.8 g), and diisopropylamine (5.3 ml) were added and stirring continued for an additional hour. After 1 h, the mixture was poured into 150 ml of ice water and extracted with 150 ml of dichloromethane. The organic solution was washed twice with water and dried over magnesium sulfate. Evaporation of solvents afforded a light purple solid (3.1 g), which was washed with hexane and filtered.

The solid was dissolved in 40 ml of dichloromethane at reflux, cooled to room temperature, and treated with tetramethylguanidine (1.6 ml), added dropwise over twenty minutes. After stirring at room temperature overnight, the mixture was cooled in an ice/salt bath and dichlorofluoromethylsulfenyl chloride (1.5 ml) was added. After 1 h, the mixture was diluted with 100 ml of methylene chloride and washed with saturated sodium bicarbonate solution, then with water, then dried over magnesium sulfate. After filtration and evaporation, chromatography on silica gel afforded 5-amino-4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole (1.285 g).

Step B

1 g of 5-amino4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole was dissolved in 15 ml of tetrahydrofuran, cooled to 0° C., and treated with t-butylnitrite. After 1 h, the mixture is evaporated. Silca gel chromatography afforded 4dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole (0.555 g).

Step C

50 mg of 4-dichlorofluoromethylsulfenyl-1-(2-fluoro-4-bromophenyl)imidazole and 37 mg of trifluoromethylphenylboronic acid in 3 ml of toluene were treated with 0.13 ml of 2M aqueous potassium carbonate and a catalytic amount (about 5 mg) of palladium tetrakis(triphenylphoshine). The mixture was heated at 90° C. for 12 h, then cooled to room temperature and evaporated. Silica gel chromatography afforded 4-dichlorofluoromethylsulfenyl-1-[2-fluoro-4-(4-trifluoromethylphenyl)phenyl]imidazole (27.3 mg, mass spec m/e 438).

In a manner similar to that employed in examples 1 to 7, the following compounds in Tables 1-4 were also prepared. The last column of the table indicates the physical characteristic of the compound obtained from the mass spectrum analysis. It is the m/e value from the mass spectrum of the molecular ion. The number of the compound is for identification only.

N/A=Not Applicable

AroCH is [4—OH 3-methoxy phenyl]—CH, so that AroCH═N— is the group [4—OH 3-methoxy phenyl]—CH═N—

TABLE 1

CMP.NO R12 R13 R15 R16 R22 R23 R24 R25 R26 R3 R4 R5 m/e 1 Cl H H Cl (CH═CH)2 H H H CN SCF3 NH2 478 2 Cl H H Cl H H H H H CN SCF3 NH2 428 3 Cl H H Cl Me H H H H CN SCF3 NH2 442 4 Cl H H Cl H NH2 H H H CN SCF3 NH2 443 5 Cl H H Cl H NO2 H H H CN SCF3 NH2 473 6 Cl H H Cl H NHAc H H H CN SCF3 NH2 485 7 Cl H H Cl H CHO H H H CN SCF3 NH2 456 8 Cl H H Cl H H OMe H H CN SCF3 NH2 458 9 Cl H H Cl H H SMe H H CN SCF3 NH2 474 10 Cl H H Cl H H F H H CN SCF3 NH2 446 11 Cl H H Cl H F H H H CN SCF3 NH2 446 12 Cl H H Cl H Cl F H H CN SCF3 NH2 480 13 Cl H H Cl H H Cl H H CN SCF3 NH2 462 14 Cl H H Cl H H Br H H CN SCF3 NH2 506 15 Cl H H Cl H Cl H Cl H CN SCF3 NH2 496 16 Cl H H Cl H H CF3 H H CN SCF3 NH2 496 17 Cl H H Cl H CF3 H CF3 H CN SCF3 NH2 564 18 Cl H H Cl (CH═CH)2 H H H CN SMe NH2 424 19 Cl H H Cl H H H H H CN SMe NH2 374 20 Cl H H Cl Me H H H H CN SMe NH2 388 21 Cl H H Cl H NH2 H H H CN SMe NH2 389 22 Cl H H Cl H NO2 H H H CN SMe NH2 419 23 Cl H H Cl H NHAc H H H CN SMe NH2 431 24 Cl H H Cl H H CHO H H CN SMe NH2 402 25 Cl H H Cl H H OMe H H CN SMe NH2 404 26 Cl H H Cl H F H H H CN SMe NH2 392 27 Cl H H Cl H Cl F H H CN SMe NH2 426 28 Cl H H Cl Cl H Cl H H CN SMe NH2 442 29 Cl H H Cl H H CF3 H H CN SMe NH2 442 30 Cl H H Cl H CF3 H CF3 H CN SMe NH2 510 31 Cl H H Cl H Br H H H CN SMe NH2 452 32 Cl H H Cl Me H H H H CN SCF3 Van-CH═N— 576 33 Cl H H Cl H NO2 H H H CN SCF3 Van-CH═N— 607 34 Cl H H Cl H NHAc H H H CN SCF3 Van-CH═N— 619 35 Cl H H Cl H H CHO H H CN SCF3 Van-CH═N— 590 36 Cl H H Cl H H OMe H H CN SCF3 Van-CH═N— 592 37 Cl H H Cl H Cl F H H CN SCF3 Van-CH═N— 614 38 Cl H H Cl Cl H Cl H H CN SCF3 Van-CH═N— 630 39 Cl H H Cl H H CF3 H H CN SCF3 Van-CH═N— 630 40 Cl H H Cl H H CF3 H H CN S(O)2CCl2F NH2 560 41 Cl H H Cl H H CF3 H H CN S(O)2CCl2F NH2 544 42 Cl H H Cl H H CF3 H H CN SCCl2F NH2 528 43 Cl H H Cl H H CF3 H H CN SOCF3 NH2 512 44 Cl H H Cl H H CF3 H H CN S(O)2CF3 NH2 528 45 Cl H H Cl H H CF3 H H PhC(O) SCF3 NH2 575 46 Cl H H Cl (CH═CH)2 H H H CN SCF3 H 463 47 Cl H H Cl H (CH═CH)2 H H CN SCF3 H 463 48 Cl H H Cl H H H H H CN SCF3 H 413 49 Cl H H Cl H NO2 H H H CN SCF3 H 458 50 Cl H H Cl H H OMe H H CN SCF3 H 443 51 Cl H H Cl H H SMe H H CN SCF3 H 459 52 Cl H H Cl H H F H H CN SCF3 H 431 53 Cl H H Cl H F H H H CN SCF3 H 431 54 Cl H H Cl H Cl F H H CN SCF3 H 465 55 Cl H H Cl H H Cl H H CN SCF3 H 447 56 Cl H H Cl H H Br H H CN SCF3 H 491 57 Cl H H Cl H Cl H Cl H CN SCF3 H 481 58 Cl H H Cl Cl H Cl H H CN SCF3 H 481 59 Cl H H Cl H H CF3 H H CN SCF3 H 481 60 Cl H H Cl H CF3 H H H CN SCF3 H 481 61 Cl H H Cl H CF3 H CF3 H CN SCF3 H 549 62 Cl H H Cl H Cl H H H CN SCF3 H 447 63 Cl H H Cl H Br H H H CN SCF3 H 491 64 Cl H H Cl H H CF3 H H PhC(O) S(O)2CCl2F NH2 639 65 Cl H H Cl H H Br H H CN SCCl2F NH2 538 66 Cl H H Cl Cl H CF3 H Cl CN SCF3 NH2 564 67 Cl H H Cl H H OCF3 H H CN SCF3 NH2 512 68 Cl H H Cl H H CF3 H H PhC(O) S(O)2CClF2 NH2 623 69 Cl H H Cl H H CF3 H H CN H NH2 396 70 Cl H H Cl H H CF3 H H CN Br NH2 474 71 Cl H H Cl H H CF3 H H CN SEt NH2 456 72 Cl H H Cl H H CF3 H H CN SMe NH2 442 73 Cl H H Cl H H CF3 H H CN SCN NH2 453 74 Cl H H Cl H H CF3 H H CN Cl NH2 430 75 Cl H H Cl H H CF3 H H CN SOMe NH2 458 76 Cl H H Cl H H CF3 H H CN S(O)Et NH2 472 77 Cl H H Cl H H Br H H CN S(O)2CCl2F NH2 570 78 Cl H H Cl H H CF3 H H CN S(O)2CH3 NH2 474 79 Cl H H Cl H H CF3 H H CN S(O)2Et NH2 488 80 Cl H H Cl H H CF3 H H CONH2 C(OH)(CF3)2 NH2 580 81 Cl H H Cl H H CF3 H H CN C(OH)(CF3)2 NH2 562 82 Cl H H Cl H H CF3 H H CN H NHAc 438 83 Cl H H Cl H H CF3 H H Ac SMe NH2 459 84 Cl H H Cl H H CF3 H H CN CF(CF3)2 NH2 564 85 Cl H H Cl H H CF3 H H CN SCCl2F H 513 86 Cl H H Cl H H CF3 H H CN S(O)2CCl2F H 545 87 Cl H H Cl H Cl Cl H H CN H NH2 396 88 Cl H H Cl H H OCF3 H H CN H NH2 412 89 Cl H H Cl F H H H H CN H NH2 346 90 Cl H H Cl H H CO2Me H H CN H NH2 386 91 Cl H H Cl H Cl Cl H H CN SCF3 NH2 496 92 Cl H H Cl F H H H H CN SCF3 NH2 446 93 Cl H H Cl H H CO2Me H H CN SCF3 NH2 486 94 Cl H H Cl H H CF3 H H CN SCCl2F Br 591 95 Cl H H Cl H H CF3 H H Ac S(O)2CH3 NH2 491 96 Cl H H Cl Cl H H H Cl CN SCF3 NH2 496 97 Cl H H Cl Cl H Cl H H CN SCF3 NH2 496 98 Cl H H Cl Cl H CF3 H Cl CN SCF3 NH2 564 99 Cl H H Cl CF3 H H H H CN SCF3 NH2 496 100 Cl H H Cl NO2 H CF3 H H CN SCF3 NH2 541 101 Cl H H Cl Me H F H H CN SCF3 NH2 460 102 Cl H H Cl H F H F H CN SCF3 NH2 464 103 Cl H H Cl F H H H F CN SCF3 NH2 464 104 Cl H H Cl H OCF3 H H H CN SCF3 NH2 512 105 Cl H H Cl H F H Cl H CN SCF3 NH2 480 106 Cl H H Cl H CN H H H CN SCF3 NH2 453 107 Cl H H Cl H OMe H H H CN SCF3 NH2 458 108 Cl H H Cl H H CH2CN H H CN SCF3 NH2 467 109 Cl H H Cl H H Ms H H CN SCF3 NH2 506 110 Cl H H Cl H H SO2NH2 H H CN SCF3 NH2 507 111 Cl H H Cl H H NMe2 H H CN SCF3 NH2 471 112 Cl H H Cl OCH2O H H H CN SCF3 NH2 472 113 Cl H H Cl H H CN H H CN SCF3 NH2 453 114 Cl H H Cl H H CN H H CN SCF3 NH2 453 115 Cl H H Cl F H F H H CN SCF3 NH2 464 116 Cl H H Cl H H CONH2 H H CN SCF3 NH2 471 117 Cl H H Cl H Cl CN H H CN SCF3 NH2 487 118 Cl H H Cl H CF3 H H H CN SCF3 NH2 496 119 Cl H H Cl F F F F F CN SCF3 NH2 518 120 Cl H H Cl H H OPh H H CN SCF3 NH2 520 121 Cl H H Cl Cl H CF3 H H CN SCF3 NH2 530 122 Cl H H Cl H OCF2O H H CN SCF3 NH2 508 123 Cl H H Cl H F NH2 H H CN SCF3 NH2 461 124 Cl H H Cl H CF3 NO2 H H CN SCF3 NH2 541 125 Cl H H Cl OH H H H H CN SCF3 NH2 444 126 Cl H H Cl H H NH2 H H CN SCF3 NH2 443 127 Cl H H Cl H H OH H H CN SCF3 NH2 444 128 Cl H H Cl H CF3 H NH2 NH2 CN SCF3 NH2 526 129 Cl H H Cl H F Me H H CN SCF3 NH2 460 130 Cl H H Cl CN F H H H CN SCF3 NH2 471 131 Cl H H Cl H Me F H H CN SCF3 NH2 460 132 Cl H H Cl Me H H F H CN SCF3 NH2 460 133 Cl H H Cl Ph H H H H CN SCF3 NH2 504 134 Cl H H Cl OH OMe H CHO H CN SCF3 NH2 502 135 Cl H H Cl H Cl Cl H H CN S(O)2CH3 NH2 474 136 Cl H H Cl Cl H H H Cl CN S(O)2CH3 NH2 474 137 Cl H H Cl Cl H Cl H H CN S(O)2CH3 NH2 474 138 Cl H H Cl Cl H CF3 H Cl CN S(O)2CH3 NH2 542 139 Cl H H Cl H H OCF3 H H CN S(O)2CH3 NH2 490 140 Cl H H Cl CF3 H H H H CN S(O)2CH3 NH2 474 141 Cl H H Cl NO2 H CF3 H H CN S(O)2CH3 NH2 519 142 Cl H H Cl Me H F H H CN S(O)2CH3 NH2 438 143 Cl H H Cl H F H F H CN S(O)2CH3 NH2 442 144 Cl H H Cl F H H H F CN S(O)2CH3 NH2 442 145 Cl H H Cl F H H H H CN S(O)2CH3 NH2 424 146 Cl H H Cl H H CF3 H H CN C═NOH NH2 439 147 Cl H H Cl H H CF3 H H CN NO2 NHAc 483 148 Cl H H Cl H H CF3 H H CN NO2 NH2 441 149 Cl H H Cl F H F H H CN S(O)2CH3 NH2 442 150 Cl H H Cl H OCF3 H H H CN S(O)2CH3 NH2 490 151 Cl H H Cl H F H Cl H CN S(O)2CH3 NH2 458 152 Cl H H Cl H H CONH2 H H CN S(O)2CH3 NH2 449 153 Cl H H Cl H CN H H H CN S(O)2CH3 NH2 431 154 Cl H H Cl H H SMe H H CN S(O)2CH3 NH2 452 155 Cl H H Cl H OMe H H H CN S(O)2CH3 NH2 436 156 Cl H H Cl H H CH2CN H H CN S(O)2CH3 NH2 445 157 Cl H H Cl H H Ms H H CN S(O)2CH3 NH2 484 158 Cl H H Cl H H SO2NH2 H H CN S(O)2CH3 NH2 485 159 Cl H H Cl H H NMe2 H H CN S(O)2CH3 NH2 449 160 Cl H H Cl OCH2O H H H CN S(O)2CH3 NH2 450 161 Cl H H Cl H Cl CN H H CN S(O)2CH3 NH2 465 162 Cl H H Cl H H CN H H CN S(O)2CH3 NH2 431 163 Cl H H Cl H H CO2Me H H CN S(O)2CH3 NH2 464 164 Cl H H Cl H CF3 H H H CN S(O)2CH3 NH2 474 165 Cl H H Cl F F F F F CN S(O)2CH3 NH2 496 166 Cl H H Cl H H OPh H H CN S(O)2CH3 NH2 498 167 Cl H H Cl Cl H CF3 H H CN S(O)2CH3 NH2 508 168 Cl H H Cl Cl H SF5 H Cl CN S(O)2CH3 NH2 600 169 Cl H H Cl Cl H OCF3 H Cl CN S(O)2CH3 NH2 558 170 Cl H H Cl H OCF2O H H CN S(O)2CH3 NH2 486 171 Cl H H Cl H CO2H OH H H CN S(O)2CH3 NH2 466 172 Cl H H Cl H F OH H H CN S(O)2CH3 NH2 440 173 Cl H H Cl H F NH2 H H CN S(O)2CH3 NH2 439 174 Cl H H Cl H CF3 NO2 H H CN S(O)2CH3 NH2 519

TABLE 2

CMP.NO R12 R13 R15 R16 R2 R22 R23 R24 R25 R26 R3 R4 R5 m/e 175 Cl H H Cl H (CH═CH)2 H H H SCFCl2 CN Cl 528 176 Cl H H Cl Cl H (CH═CH)2 H H CN SCFCl2 H 528 177 Cl H H Cl Cl H H H H H CN SCFCl2 H 478 178 Cl H H Cl H H H Me H H SCFCl2 CN Cl 492 179 Cl H H Cl H Me H H H H SCFCl2 CN Cl 492 180 Cl H H Cl Cl H NH2 H H H CN SCFCl2 H 493 181 Cl H H Cl H H NO2 H H H SCFCl2 CN Cl 523 182 Cl H H Cl Cl H NHAc H H H CN SCFCl2 H 535 183 Cl H H Cl H CHO H H H H SCFCl2 CN Cl 506 184 Cl H H Cl H H CHO H H H SCFCl2 CN Cl 506 185 Cl H H Cl Cl H H CHO H H CN SCFCl2 H 506 186 Cl H H Cl H OMe H H H H SCFCl2 CN Cl 508 187 Cl H H Cl H H OMe H H H SCFCl2 CN Cl 508 188 Cl H H Cl Cl H H OMe H H CN SCFCl2 H 508 189 Cl H H Cl Cl H H SMe H H CN SCFCl2 H 524 190 Cl H H Cl H H H F H H SCFCl2 CN Cl 496 191 Cl H H Cl Cl H F H H H CN SCFCl2 H 496 192 Cl H H Cl Cl H Cl F H H CN SCFCl2 H 530 193 Cl H H Cl H H H Cl H H SCFCl2 CN Cl 512 194 Cl H H Cl H H H Br H H SCFCl2 CN Cl 556 195 Cl H H Cl Cl H Cl H Cl H CN SCFCl2 H 546 196 Cl H H Cl H Cl H Cl H H SCFCl2 CN Cl 546 197 Cl H H C1 Cl H H CF3 H H CN SCFCl2 H 546 198 Cl H H Cl Cl H CF3 H H H CN SCFCl2 H 546 199 Cl H H Cl H H CF3 H CF3 H SCFCl2 CN Cl 614 200 Cl H H Cl Cl H Cl H H H CN SCFCl2 H 512 201 Cl H H Cl Cl H Br H H H CN SCFCl2 H 556 202 Cl H H Cl H H H CF3 H H S(O)CFCl2 CN Cl 562 203 Cl H H Cl H H H CF3 H H S(O)2CFCl2 CN Cl 578 204 H H H H H H H CF3 H H CHO H H 315 205 H H H Me H H H CF3 H H CHO H H 329 206 Me H H Me H H H CF3 H H CHO H H 343 207 Cl H H H H H H CF3 H H CHO H H 349 208 H Cl H H H H H CF3 H H CHO H H 349 209 Cl H H Me H H H CF3 H H CHO H H 363 210 Cl H H Cl H H H CF3 H H CHO H H 383 211 F H H H H H H CF3 H H CHO H H 333 212 F H H F H H H CF3 H H CHO H H 351 213 H H H CF3 H H H CF3 H H CHO H H 383 214 H H CF3 H H H H CF3 H H CHO H H 383 215 F F F F H H H CF3 H H CHO H H 387 216 Me H H NO2 H H H CF3 H H CHO H H 374 217 H H (CH═CH)2 H H H CF3 H H CHO H H 365

TABLE 3

CMP.NO R12 R13 R15 R16 R22 R23 R24 R25 R26 R3 R5 m/3 218 Cl H H Cl H H CF3 H H t-Bu NH2 428 219 Cl H H Cl H H CF3 H H t-Bu H 413 220 Cl H H Cl H H CF3 H H t-Bu Br 491 221 Cl H H Cl H H CF3 H H CF3 NH2 440 222 Cl H H Cl H NO2 H H H CF3 NH2 417 223 Cl H H Cl H F H H H CF3 NH2 390 224 Cl H H Cl H H CF3 H H CF3 Br 503 225 Cl H H Cl H H CF3 H H CF3 H 425 226 Cl H H Cl H (CH═CH)2 H H CF3 NH2 422 227 Cl H H Cl (CH═CH)2 H H H CF3 NH2 422 228 Cl H H Cl Me H H H H CF3 NH2 386 229 Cl H H Cl H OMe H H H CF3 NH2 402 230 Cl H H Cl H H OMe H H CF3 NH2 402 231 Cl H H Cl H H SMe H H CF3 NH2 418 232 Cl H H Cl H H F H H CF3 NH2 390 233 Cl H H Cl H H Cl H H CF3 NH2 406 234 Cl H H Cl H H Br H H CF3 NH2 450 235 Cl H H Cl H Cl H Cl H CF3 NH2 440 236 C1 H H Cl Cl H Cl H H CF3 NH2 440 237 Cl H H Cl H CF3 H H H CF3 NH2 440 238 Cl H H Cl H Cl H H H CF3 NH2 406 239 Cl H H Cl H Br H H H CF3 NH2 450 240 Cl H H Cl (CH═CH)2 H H H CF3 H 407 241 Cl H H Cl H H H H H CF3 H 357 242 Cl H H Cl H H Me H H CF3 H 371 243 Cl H H Cl H NO2 H H H CF3 H 402 244 Cl H H Cl H CHO H H H CF3 H 385 245 Cl H H Cl H OMe H H H CF3 H 387 246 Cl H H Cl H H F H H CF3 H 375 247 Cl H H Cl H H F H H CF3 H 375 248 Cl H H Cl H F H H H CF3 H 375 249 Cl H H Cl H Cl F H H CF3 H 409 250 Cl H H Cl H (CH═CH)2 H H CF3 H 407 251 Cl H H Cl H NHAc H H H CF3 H 414 252 Cl H H Cl CHO H H H H CF3 H 385 253 Cl H H Cl H H CHO H H CF3 H 385 254 Cl H H Cl OMe H H H H CF3 H 387 255 Cl H H Cl H H CF3 H H SMe H 403 256 Cl H H Cl H H CF3 H H SMe NH2 418 257 Cl H H Cl H H CF3 H H SOMe NH2 434 258 Cl H H Cl H H CF3 H H SOMe H 419 259 Cl H H Cl H H CF3 H H SOMe Br 497 260 Cl H H Cl H H CF3 H H SCCl2F H 489 261 Cl H H Cl H H CF3 H H S(O)CCl2F H 505 263 Cl H H Cl H H CF3 H H S(O)2CCl2F H 521

TABLE 4

CMP.NO R12 R13 R15 R16 R21 R23 R24 R25 R26 R4 R5 m/e 264 Cl H H Cl H H CF3 H H SCCl₂F H 488 265 Cl H H Cl H H CF3 H H SCCl₂F Br 566 266 Cl H H Cl H H CF3 H H SCCl₂F NH2 503 267 Cl H H Cl H H CF3 H H SO₂CCl2F Br 537 268 Cl H H Cl H H CF3 H H SOCCl₂F H 504 269 Cl H H Cl H H CF3 H H SO2CCl2F H 520 270 H H H F H H CF3 H H SOCC12F H 454 271 Cl H H Cl Cl H CF3 H Cl SOCCl2F H 572 272 Cl H H Cl H H OCF3 H H SOCCl2F H 520 273 Cl H H Cl H OCF2O H H SOCCl2F H 516 274 Cl H H Cl H H H H H SOCCl2F H 436 275 Cl H H Cl Me H Me Me H SOCCl2F H 478 276 Cl H H Cl Me H H H Me SOCCl2F H 464 277 Cl H H Cl H H t-Bu H H SOCCl2F H 492 278 Cl H H Cl H CF3 H CF3 H SOCCl2F H 572 279 Cl H H Cl H CH2CN H H H SOCCl2F H 475 280 Cl H H Cl H OCH2O H H SOCCl2F H 480 281 Cl H H Cl H F H F H SOCCl2F H 472 282 Cl H H Cl F F NH2 F F SOCCl2F H 523 283 Cl H H Cl NO2 H CF3 H H SOCCl2F H 549 284 Cl H H Cl H H CH2CN H H SOCCl2F H 475 285 Cl H H Cl H H n-Bu H H SOCCl2F H 492 286 Cl H H Cl Cl H Cl H H SOCCl2F H 504 287 Cl H H Cl H NO2 NH2 Me Me SOCCl2F H 524 288 Cl H H Cl Cl H CF3 H H SOCCl2F H 538 289 Cl H H Cl Cl H Cl H Cl SOCCl2F H 538 290 Cl H H Cl F F CF3 F F SOCCl2F H 576 291 Cl H H Cl F F CN F F SOCCl2F H 533 292 Cl H H Cl 5-tetrazolyl H H H H SOCCl2F H 504 293 Cl H H Cl H H CN H H SOCCl2F H 461 294 Cl H H Cl Cl H SF5 H Cl SOCCl2F H 630 295 H H H F H H CF3 H H SCCl2F H 438 296 Cl H H Cl H H CF3 H H SCF3 H 456 297 Cl H H Cl H H CF3 H H SOCF3 H 472 298 Cl H H Cl H H CF3 H H SO₂CF3 H 488

The present invention provides also a method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of a compound of formula (I), or a pesticidal composition comprising a pesticidally effective amount of a compound of formula (I) and a pesticidally acceptable carrier therefor. In a preferred embodiment, the invention provides a method for controlling insects at a locus comprising applying to said locus an insecticidally effective amount of a compound of formula (I), or an insecticidally effective amount of an insecticidal. composition comprising an insecticidally effective amount of a compound of formula (I) and an agriculturally acceptable inert carrier therefor. Preferably, the locus to which the pesticidally (especially insecticidally) effective amount is applied is a crop-growing area, that is, an area in which a crop is growing or in which a crop has been planted, or an area in which a crop will be planted/grown.

The compositions which can be used in the invention for the pesticidall insecticidal treatment of the invention can comprise from about 0.001 to 95% of the compound of formula (I).

The diluted liquid formulations, as applied to the locus to be treated or crop, generally comprise from about 0.001 to about 3% of active ingredient of formula (I), preferably from about 0.1 to about 0.5%.

The solid formulations as applied to the locus or crop generally comprise from about 0.1 to about 8% of active ingredient of formula (I), preferably from about 0.5 to about 1.5%.

The concentrated compositions are the compositions which are commercialized or transported or stored. For application to plants, they are normally diluted in water and applied in such diluted form. The diluted forms are part of the invention as well as the concentrated forms.

The concentrated formulations generally comprise from about 5 to about 95% of active ingredient of formula (I), preferably from about 10 to about 50%.

The insecticidal compositions of the invention can be applied once, or more than once, throughout the whole insect season. Insecticidal compositions according to the invention are usually applied to the locus to be treated or crop area at a rate of from about 0.01 to about 2 kg/ha of active ingredient, preferably from about 0.1 to about 1 kg/ha.

The concentrated insecticidal compositions according to the invention can be in the form of a solid, e.g., dusts or granules or wettable powders, or, preferably, in the form of a liquid, such as an emulsifiable concentrate or a true solution.

The compositions according to the instant invention generally comprise from about 0.5 to about 95% of active ingredient of formula (I). The remainder of the composition up to 100% comprises a carrier as well as various additives such as those hereafter indicated.

By “carrier”, there is meant herein an organic or inorganic material, which can be natural or synthetic, and which is associated with the active ingredient and which facilitates its application to the locus to be treated or crop. This carrier is thus generally inert and should be agriculturally acceptable, especially on the contemplated or treated locus or crop. The carrier can be solid (clay, silicates, silica, resins, wax, fertilizers, etc.) or liquid (water, alcohols, ketones, oil solvents, saturated or unsaturated hydrocarbons, chlorinated hydrocarbons, liquified petroleum gas, etc.).

Among the many additives, the compositions of the invention can comprise surfactants as well as other ingredients such as dispersants, stickers, antifoam agents, antifreezing agents, dyestuffs, thickeners, adhesives, protective colloids, penetrating agents, stabilizing agents, sequestering agents, antiflocculating agents, corrosion inhibitors, pigments and polymers.

More generally, the compositions of the invention can comprise all kinds of solid or liquid additives which are known in the art of insecticides and insecticidal treatments.

The surfactants can be of the emulsifying or wetting type, ionic or non-ionic. Possible surfactants are salts of polyacrylic or lignosulfonic acids; salts of phenolsulfonic or naphthalenesulfonic acids; polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines or substituted phenols (particularly alkylphenols or arylphenols); ester-salts of sulfosuccinic acids; taurine derivatives, such as alkyl taurates; phosphoric esters; or esters of alcohols or polyoxyethylated phenols. When the spraying vehicle is water, the use of at least one surfactant is generally required because the active ingredients are not water-soluble.

The method of application of the compositions of the invention is generally the spraying of a mixture which has been previously made, by dilution of more concentrated formulations according to the invention.

Solid compositions can be powders for dusting or for dispersion (wherein the content of active ingredient can be up to 100%) and granules, especially extruded or compacted granules, or granules which have been made by impregnation of a powder (the content of active ingredient in such powders being between about 1 and about 80%).

Liquid compositions or compositions which have to be liquid when applied include solutions, water-soluble concentrates, emulsifiable concentrates, emulsions, wettable powders or pastes or water-dispersible granules.

Emulsifiable concentrates generally comprise from about 10 to about 80% of active ingredient; the emulsions when applied Generally comprise from about 0.01 to about 20% of active ingredient.

For example, the emulsifiable concentrates can comprise the solvent and, to the extent needed, from about 2 to about 20% of suitable additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors or other additives already recited.

These concentrates are usually diluted in tank water so as to obtain the dilution appropriate for spraying.

The concentrated suspensions can also be applied by spraying and have to be fluid without allowing any solid to separate and fall to the bottom. Generally they comprise from about 1 to about 75% of active ingredient (preferably from about 2 to about 50%), from about 0.5 to about 15% of surfactant, from about 0.1 to about 10% of thickener, from 0 to about 10% of other suitable additives as already indicated, the remainder being water or an organic liquid wherein the active ingredient is insoluble or has a low solubility.

The wettable powders generally comprise the active ingredient (from about 1 to about 95%, preferably from about 2 to about 80%), the solid carrier, a wetting agent (from 0 to about 5%), a dispersing agent (from about 3 to about 10%) and, to the extent needed, from 0 to about 10% of other additives such as stabilizers and others as already listed.

In order to obtain these wettable powders or dusting powders, it is appropriate to intimately mix the active ingredients and the additives, as by grinding in a mill or similar device.

Dispersible granules are generally made by agglomeration of a powder, followed by an appropriate granulation process.

The emulsions herein described can be of the oil-in-water or water-in-oil types. Fluidity of the emulsions can range from low viscosities up to high viscosities approaching those of gels.

Among these many compositions or formulations, one skilled in the art can choose the one most appropriate, according to the specific conditions of the treatment problem.

The compounds and compositions of the invention can also be used in admixtures with another pesticide, e.g., an insecticide, acaricide or herbicide.

The compounds of the invention may also be used in controlling pests found in non-agricultural domains.

In the field of veterinary medicine or livestock husbandry or in the maintenance of public health against arthropods, helminths or protozoa which are parasitic internally or externally upon vertebrates, particularly warm-blooded vertebrates, for example man or domestic animals, e.g. cattle, sheep, goats, equines, swine, poultry, dogs or cats, for example Acarina, including ticks (e.g. Ixodes spp., Boophilus spp. e.g. Boophilus microplus, Amblyomma spp., Hyalomma spp., Rhipicephalus spp. e.g. Rhipicephalus appendiculatus, Haemaphysalis spp., Dermacentor spp., Ornithodorus spp. (e.g. Ornithodorus moubata) and mites (e.g. Damalinia spp., Dermahyssus gallinae, Sarcoptes spp. e.g. Sarcoptes scabiei, Psoroptes spp., Chorioptes spp;, Demodex spp., Eutrombicula spp.,); Diptera (e.g. Aedes spp., Anopheles spp., Dermatobia spp., Haematobia spp., Musca spp., Hippoboscidae spp., Hypoderma spp., Gasterophilus spp., Simulium spp); Stomoxys spp., Hemiptera (e.g. Triatoma spp); Phthirapter (e.g. Damalinia spp., Linognathus spp.); Siphonaptera (e.g. Ctenocephalides spp.); Dictyoptera (e.g. Periplaneta spp., Blatella spp.); Hymenoptera (e.g. Monomorium pharaonis); for example against infections of the gastro-intestinal tract caused by parasitic nematode worrns, for example members of the family Trichostrongylidae, Nippostrongylus brasiliensis, Trichinella spiralis, Haemonchus contortus, Trichostrongylus colubriformis, Nematodirus batus, Ostertagis circumcincta, Trichostrongylus axei, Cooperia spp. and Hymenolepis nana; in the control and treatment of protozoal diseases caused by, for example, Eimeria spp. e.g. Eimeria tenella, Eimeria acervulina, Eimeria brunetti, Eimeria maxima and Eimeria necatrix, Trypanosoms cruzi, Leishaminia spp., Plasmodium spp., Babesis spp., Trichomonadidae spp., Histomanas spp., Giardia spp., Toxoplasma spp., Entamoeba histolytica and Theileria spp.

Furthermore the compounds of the invention may be useful for coccidiosis, a disease caused by infections from protozoan parasites of the genus Eimeria.

Compositions

Solid or liquid compositions for application topically to animals, timber, stored products or household goods usually contain from about 0.00005% to about 90%, more particularly from about 0.001% to about 10%, by weight of one or more compounds of general formula (I). For administration to animals orally or parenterally, including percutaneously solid or liquid compositions, these normally contain from about 0.1% to about 90% by weight of one or more compounds of general formula (I). Medicated feedstuffs normally contain from about 0.001% to about 3% by weight of one or more compounds of general formula (I). Concentrates or supplements for mixing with feedstuffs normally contain from about 5% to about 90%, preferably from about 5% to about 50%, by weight of one or more compounds of general formula (I). Mineral salt licks normally contain from about 0.1% to about 10% by weight of one or more compounds of general formula (I).

Dusts or liquid compositions for application to livestock, persons, goods, premises or outdoor areas may contain from about 0.0001% to about 15%, more especially from about 0.005% to about 2.0%, by weight, of one or more compounds of general formula (I). Suitable concentrations in treated waters are between about 0.0001 ppm and about 20 ppm, more particularly about 0.001 ppm to about 5.0 ppm of one or more compounds of general formula (I) and may be used therapeutically in fish farming with appropriate exposure times. Edible baits may contain from about 0.01% to about 5%, preferably from about 0.01% to about 1.0%, by weight, of one or more compounds of general formula (I).

When administered to vertebrates parenterally, orally or by percutaneous or other means, the dosage of compounds of general formula (I) will depend upon the species, age, or health of the vertebrate and upon the nature and degree of its actual or potential infestation by arthropod, helminth or protozoan pests. A single dose of about 0.1 to about 100 mg, preferably about 2.0 to about 20.0 mg, per kg body weight of the animal or doses of about 0.01 to about 20.0 mg, preferably about 0.1 to about 5.0 mg, per kg body weight of the animal per day, for sustained medication, are generally suitable by oral or parenteral administration. By use of sustained release formulations or devices, the daily doses required over a period of months may be combined and administered to animals on a single occasion.

The following methods were used to apply the compounds of the invention and to observe the results obtained therewith: a foliar/contact spray on sucking (aphids) or chewing (Lepidoptera) insects.

The species tested were as folllows:

GENUS, SPECIES COMMON NAME Aphis gossypii cotton leaf aphid Musca domestica housefly Diabrotica virgifera Western comrootworm Periplaneta americana American Cockroaches Spodoptera eridania Southern armyworm

The Housefly Bait/Contact Test

About 25 four to six-day-old adult houseflies were anesthetized and placed in a cage with a sugar water bait solution containing the compound. The concentration of the selected compound of formula (I) in the bait solution was 50 ppm. After 24 hours, flies which showed no movement on stimulation were considered dead.

Foliar Application (Contact Test) with Aphids

Aphid-infested cotton plants were placed on a revolving turntable, and sprayed to runoff with a 100 ppm formulation of the selected compound of formula (I). The treated, A. gossypii-infested plants were held for three days after treatment, after which the dead aphids were counted.

Application on Western Cornrootworm

Jars are filled with 60 g dry soil homogeneously mixed with 5 ml aqueous solution containing the compound to be tested. After drying, four germinated corn seedlings are placed in the bottom of each jar and the soil is wetted. Then ten newly born larvae are placed in each jar. The jars are stored for six days at 27° C. under 70% of relative humidity. The number of surviving larvae are then counted.

Application by Contact to Cockroaches

The inner wall of a 100 ml jar is covered by shaking 2 ml of pesticidal formulation. Furthermore, a pellet of dog chow is placed into a jar and the pesticidal formulation is absorbed on the pellet, using excess liquid. The jar is then left open up to evaporation of liquid. Cockroach nymphs are placed in the jar and mortality is assessed after five days.

Application to Southern Armyworm

Leaves of soybeans were sprayed to run-off with a spray of various concentrations. Then the leaves were allowed to dry, excised, and placed into a container with five larvae. The containers are stored for five days at 25° C. under 50% relative humidity. Mortality ratings are then counted.

Application to Caenorhabditis elegans (nematode worm)

This test is significative for animal health applications of active ingredient.

Test formulation are prepared by mixing 2 microliters of dimethylsulfoxide with 100 microliters of a solution of Escherichia Coli (which is food for C.elegans). 98 microliters of this mixture are then mixed with an inoculum solution which consists of mixed life stages of C.Elegans (about 50 worms). This new mixture is stored 7 days at 20° C. Mortality is then visually assessed as well as the behavior of the worm. For the mortality, the rating is either 1 (large increase in number of the population, similar to the control which is trebbling in 7 days) or 3 (slight increase of the population, but significantly less increase than the control) or 5 (little to no increase in the population). For the behavior effect, the rating is either 1 (normal motion) or 3 (motion is slower than the control) or 5 (little to no movement).

All the hereinabove prepared compounds show a positive activity in one or more of these tests (rather good activity on C. elegans).

While the invention has been described in terms of various preferred embodiments, the person skilled in the art will appreciate that various modifications, substitutions, omissions and changes can be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by the scope of the following claims, including equivalents thereof. 

What is claimed is:
 1. A compound having the formula:

wherein: R₃ is CN; R₄ is H, halogen, alkyl, alkoxy, CN, NO₂, haloallyl, haloalkoxy, thiocyanato, formyl, allylcarbonyl, —CH═N—OH, —CH═N—O-alkyl, —S(NH₂)(═NH), mercapto, haloalkylcarbonyl, or a —S— radical so that two molecules are bound together to form a disulfide compound, R₅ is —NR₉R₁₀; R₉ and R₁₀, independently of each other, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈S(O)_(n), formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, or aroyl; or R₉ and R₁₀ are joined so as to together form a divalent radical having 4 to 6 atoms in the chain, said divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, the alkyl portions of R₉ and R₁₀ being optionally substituted by R₇; R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈S(O)_(n), —C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, —CO₂H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; R₈ is alkyl, haloalkyl, alkenyl or alkynyl, or R₈ is a cycloalkyl ring having 3 to 5 carbon atoms; Z is N or C—R₁₆; n is zero, one or two; R₁₂, R₁₃, R₁₅ and R₁₆, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl or alkoxycarbonyl; and R₂₂, R₂₃, R₂₄, R₂₅, and R₂₆, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, alkoxycarbonyl, SF₅, or R₈S(O)_(n); or R₂₂ and R₂₃ or R₂₃ and R₂₄ or R₂₅ and R₂₆ together form divinylidene (CH═CH—CH═CH—), methylenedioxy (—O—CH₂—O—) or difluoromethylenedioxy (—O—CF₂—O—) so as to form a cyclic ring vicinal to the phenyl ring; or a pesticidally acceptable salt thereof.
 2. A compound according to claim 1, wherein R₉ and R₁₀ are joined together to form with the adjacent nitrogen atom a morpholine, pyrrolidine, piperidine or piperazine ring, optionally substituted by R₇.
 3. A compound according to claim 1, wherein R₂₄ is halogen, haloalkyl or haloalkoxy.
 4. A compound according to claim 1, wherein R₅ is —NH₂.
 5. A compound according to claim 1, wherein R₈ is lower alkyl or haloalkyl.
 6. A compound having formula (I) according to claim 1, wherein: R₄ is H, halogen, alkyl, alkoxy, CN, NO₂, haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, —CH═N—OH, —CH═N—O-alkyl, —S(NH₂)(═NH), mercapto or haloalkylcarbonyl; R₉ and R₁₀, independently of each other, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈—S(O)_(n), formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, or aroyl, the alkyl portions of R₉ and R₁₀ being optionally substituted by R₇; and R₂₂, R₂₃, R₂₄, R₂₅, and R₂₆, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, alkoxycarbonyl, SF₅, or R₈S(O)_(n); or a pesticidally acceptable salt thereof.
 7. A compound according to claim 6, wherein R₅ is —NH₂.
 8. A compound according to claim 6, wherein R₈ is lower alkyl or haloalkyl.
 9. A compound according to claim 6, wherein R₂₄ is halogen, haloalkyl or haloalkoxy.
 10. A compound according to claim 1, having at least one feature selected from the group consisting of: R₄ is H, halogen or formyl; R₈ is methyl, ethyl, —CF₃, CFCl₂, or —CF₂Cl; R₁₂ and R₁₆, independently of each other, are F, Cl, Br or H; R₁₃ and R₁₅ are H; R₂₄ is —CF₃, —OCF₃, —CHF₂, —S(O)_(n)CF₃, —CFCl₂, —CF₂Cl, —OCF₂Cl, —OCFCl₂, Cl, Br or F; and Z is CCl, CF, CBr or N.
 11. A compound according to claim 10, wherein R₅ is —NH₂.
 12. A compound according to claim 1, wherein the S(O)_(n)R₈ substituent of formula (I) is: methylthio, methylsulfinyl, methylsulfonyl, ethylsulfinyl, ethylsulfonyl, ethylthio, cyclopropylsulfinyl, cyclopropylthio, cyclopropylsulfonyl, isopropylsulfinyl, isopropylsulfonyl, isopropylthio, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
 13. A compound according to claim 10, wherein the S(O)_(n)R₈ substituent of formula (I) is: trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, dichlorofluoromethylthio, dichlorofluoromethylsulfinyl, dichlorofluoromethylsulfonyl, chlorodifluoromethylthio, chlorodifluoromethylsulfonyl or chlorodifluoromethylsulfinyl.
 14. The compound of formula (I) according to claim 1, which is: 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-5-aminopyrazole; or 1-[2,6-dichloro-4-(4-trifluoromethylphenyl)phenyl]-3-cyano-4-bromo-5-aminopyrazole.
 15. A pesticidal composition comprising: (a) a pesticidally effective amount of a compound having the formula:

 wherein: R₃ is CN; R₄ is H, halogen, alkyl, alkoxy, CN, NO₂, haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, —CH═N—OH, —CH═N—O-alkyl, —S(NH₂)(═NH), mercapto, haloalkylcarbonyl, or a —S— radical so that two molecules are bound together to form a disulfide compound; R₅ is —NR₉R₁₀; R₉ and R₁₀, independently of each other, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈S(O)_(n), formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, or aroyl; or R₉ and R₁₀ are joined so as to together form a divalent radical having 4 to 6 atoms in the chain, said divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, the alkyl portions of R₉ and R₁₀ being optionally substituted by R₇; R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈S(O)_(n), —C(O)alkyl, alkoxycarbonyl, amninocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, —CO₂H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; R₈ is alkyl, haloalkyl, alkenyl or alkynyl, or R₈ is a cycloalkyl ring having 3 to 5 carbon atoms; Z is N or C—R₁₆; n is zero, one or two; R₁₂, R₁₃, R₁₅ and R₁₆, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl or alkoxycarbonyl; and R₂₂, R₂₃, R₂₄, R₂₅, and R₂₆, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, alkoxycarbonyl, SF₅, or R₈S(O)_(n); or R₂₂ and R₂₃ or R₂₃ and R₂₄ or R₂₅ and R₂₆ together form divinylidene (CH═CH—CH═CH—), methylenedioxy (—O—CH₂—O—) or difluoromethylenedioxy (—O—CF₂—O—) so as to form a cyclic ring vicinal to the phenyl ring; or a pesticidally acceptable salt thereof; and (b) a pesticidally acceptable carrier therefor.
 16. A composition according to claim 15, comprising from 0.001 to 9.5% of compound of formula (I).
 17. A method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of a compound having the formula:

wherein: R₃ is CN; R₄ is H, halogen, alkyl, alkoxy, CN, NO₂, haloalkyl, haloalkoxy, thiocyanato, formyl, alkylcarbonyl, —CH═N—OH, —CH═N—O-alkyl, —S(NH₂)(═NH), mercapto, haloalkylcarbonyl, or a —S— radical so that two molecules are bound together to form a disulfide compound; R₅ is —NR₉R₁₀; R₉ and R₁₀, independently of each other, are H, alkyl, haloalkyl, alkylcarbonyl, haloalkylcarbonyl, R₈S(O)_(n), formyl, alkenyl, alkynyl, alkoxycarbonyl, alkylthiocarbonyl, or aroyl; or R₉ and R₁₀ are joined so as to together form a divalent radical having 4 to 6 atoms in the chain, said divalent radical being alkylene, alkyleneoxyalkylene or alkyleneaminoalkylene, the alkyl portions of R₉ and R₁₀ being optionally substituted by R₇; R₇ is cyano, nitro, alkoxy, haloalkoxy, R₈S(O)_(n), —C(O)alkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, —CO₂H, halogen, hydroxy, aminosulfonyl, alkylaminosulfonyl or dialkylaminosulfonyl; R₈ is alkyl, haloalkyl, alkenyl or alkynyl, or R₈ is a cycloalkyl ring having 3 to 5 carbon atoms: Z is N or C—R₁₆; n is zero, one or two; R₁₂, R₁₃, R₁₅ and R₁₆, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, alkylsulfenyl, alkylsulfinyl, alkylsulfonyl, haloalkylsulfenyl, haloalkylsulfinyl, haloalkylsulfonyl, formyl, alkylcarbonyl or alkoxycarbonyl; and R₂₂, R₂₃, R₂₄, R₂₅, and R₂₆, independently of one another, are hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, cyano, nitro, amino, hydrazino, alkoxy, haloalkoxy, haloalkylcarbonyl, formyl, alkylcarbonyl, thioamide, amide, alkoxycarbonyl, SF₅, or R₈S(O)_(n); or R₂₂ and R₂₃ or R₂₃ and R₂₄ or R₂₅ and R₂₆ together form divinylidene (CH═CH—CH═CH—), methylenedioxy (—O—CH₂—O—) or difluoromethylenedioxy (—O—CF₂—O—) so as to form a cyclic ring vicinal to the phenyl ring; or a pesticidally acceptable salt thereof.
 18. A method according to claim 17, wherein said pests are insects and wherein said pesticidally effective amount is an insecticidally effective amount.
 19. A method according to claim 18, comprising applying to said locus from about 0.01 to about 2 kg/ha of compound of formula (I).
 20. A method according to claim 19, comprising applying to said locus from about 0.1 to about 1 kg/ha of compound of formula (I).
 21. A method for controlling pests at a locus comprising applying to said locus a pesticidally effective amount of a composition as claimed in claim
 15. 22. A method according to claim 21, wherein said pests are insects aid wherein said pesticidally effective amount is an insecticidally effective amount.
 23. A process for preparing a compound of formula (I) according to claim 1, which comprises: (a) reacting a compound of formula (II):

wherein R₃, R₄, R₅, Z, R₁₂, R₁₃ and R₁₅ are as defined in claim 1, with a boric acid or ester in the presence of a coupling catalyst to form a compound of formula (III):

wherein R₃, R₄, R₅, Z, R₁₂, R₁₃ and R₁₅ are as defined in claim 1 and R₃₀ is hydrogen, alkyl, or divalent lower alkylene such that B(OR₃₀)₂ forms a cyclic borate ester; followed by reacting the resultant compound of formula (III) with a compound of formula (VI):

wherein R₂₂, R₂₃, R₂₄, R₂₅ and R₂₆ are as defined in claim 1 and R₂₀ is bromine, iodine or O—SO₂CF₃; (b) reacting a compound of formula (II) above with a compound of formula (IV):

wherein R₂₂, R₂₃, R₂₄, R₂₅, and R₂₆ are as defined in claim 1 and R₃₀ is as defined above; (c) reacting a compound of formula (II) above with a hexaalkylstannane to form a compound of formula (V):

wherein R₃, R₄, R₅, Z, R₁₂, R₁₃, and R₁₅ are as defined in claim 1; followed by reacting the resultant compound of formula (V) with a compound of formula (IV) above in the presence of a coupling catalyst; or (d) reacting a compound of formula (II) above with a compound of formula (VI) above in the presence of a coupling catalyst. 